CN101589125A - The blooming of binder composition and band tackiness agent - Google Patents

Abstract

The invention provides a kind of binder composition, it contains (A) acrylic resin, (B) linking agent, (C) following formula Y _aR ¹ _bSi (OCH ₃) _c(OC ₂H ₅) _d(OR ²) _e(OH) _fO _{(4-a-b-c-d-e-f)/2}(Y is the organic group more than a kind that has in selected from mercapto, epoxy group(ing), (methyl) acryloxy, thiazolinyl, haloalkyl and the amino; R ¹It is the monovalence alkyl that does not have the non-replacement of aliphatics unsaturated link(age) more than a kind; R ²Be the alkyl or the methoxy-propyl of carbonatoms 3 and/or 4; A, b, c, d, e and f are the organopolysiloxane of the number of satisfied 0.01≤a≤1,0≤b＜2,0＜c≤2,0≤d≤2,0＜e≤2,0≤f≤1 and 0.1≤c+d+e≤2.5 and 2≤a+b+c+d+e+f≤3.Composition of the present invention it is being pasted on the blooming, make under the state of blooming of band tackiness agent, it is stable that performance keeps for a long time, even and the maximization re-workability also good, weather resistance is also excellent simultaneously.

Description

The blooming of binder composition and band tackiness agent

Technical field

The present invention relates to binder composition and particularly be fitted in the blooming of liquid-crystal display with the band tackiness agent that uses on the glass case.

Background technology

Normally used liquid crystal cell has liquid crystal composition and is clamped in two structures between the glass substrate in TN (Twisted Nematic), the STN liquid crystal indicators such as (Super Twisted Nematic).And the surface of each glass substrate is situated between has bloomings such as polarizing coating, phase retardation film by the adhesive laminated that with the acrylic resin is main component.Therefore, blooming is usually with the form circulation of the blooming of the band tackiness agent that is formed with binder layer on its at least one face, and in the stage of assembling liquid crystal cell, adopts usually its binder side is fitted in form on the glass substrate.

The blooming of such band tackiness agent, because big by the flexible dimensional change that causes under heat or wet heat condition, therefore, when being fitted in the state of the optical laminate on the glass substrate, there is following problem: bubble in the binder layer, or produce loosening (floating I) between binder layer and the glass substrate, peel off etc.And, recently,, also bring into use liquid crystal indicator, in vehicle-mounted purposes, even such weather resistance such as also require under hot and humid condition, also not produce foaming, become flexible, peel off as vehicle mounteds such as auto-navigation systems.

In addition, the blooming of band tackiness agent is fitted in liquid-crystal display with on the glass case time, exist under the situation of defective, heavily paste once more after peeling off this blooming, but when it is peeled off, also require binder layer and blooming together be stripped from, on glass substrate not the residual adhesive layer, do not produce so-called re-workabilities such as fuzzy.Recently, be accompanied by the maximization of TV purposes etc., the area of blooming is also becoming greatly, begins requirement than more excellent in the past re-workability.

In order to address these problems, to being that the tackiness agent of main component has proposed various schemes with the acrylic resin.For example, in No. 3022993 communique of special permission (patent documentation 1), record on the surface of polarizing coating the acrylic resin adhesive layer that contains the silane compound with epoxy group(ing) is set.In addition, in special permission No. 3487940 communique (patent documentation 2), record the binder composition that in acrylic resin, is combined with solidifying agent and specific silicon ester oligopolymer, also record in the bloomings such as this binder composition being applicable to polarizing coating.

Patent documentation 1: specially permit No. 3022993 communique (spy opens flat 4-223403 communique)

Patent documentation 2: specially permit No. 3487940 communique (spy opens flat 8-199130 communique)

Disclosure of an invention

The problem that invention will solve

But, the inventor etc. study, the result is clear and definite, the known in the past blooming that is provided with tackiness agent, if behind the applying adhesive about 3 months, re-workability, adhesion durability after Jie is fitted on the glass substrate by its binder layer are better, but after the coating during through half a year or 1 year long-time, the adhesion durability, the re-workability that are situated between after being fitted on the glass substrate by its binder layer reduce sometimes.

Therefore, the objective of the invention is to, provide preferably as the binder composition of the tackiness agent of blooming and the blooming that uses its band tackiness agent, wherein, the blooming re-workability of described band tackiness agent is good, in the time of simultaneously can suppressing to be fitted on the glass substrate between glass substrate and the binder layer become flexible, peel off and binder layer in foaming, behind the applying adhesive, such become flexible, peel off, bubble, blur etc., weather resistance and re-workability excellence even also be difficult for producing through half a year or 1 year long-time.

In order to solve above-mentioned problem, the inventor etc. have carried out deep research, found that, and be that the tackiness agent of neccessary composition is effective with the organopolysiloxane that contains organo-functional groups such as the sulfydryl multiple alkoxyl group different at a part with carbonatoms.

That is, for silane compound that in adhesive field, used and even organopolysiloxane in the past, though have a lot of of methoxyl group and/or oxyethyl group at intramolecularly, its water-disintegrable can not fully control in this case, storage stability has problems.Acrylic adhesive particularly owing to contain moisture, therefore be difficult to make the tackiness agent that contains silane compound long-term between as the stable in properties of tackiness agent.Therefore the organopolysiloxane of finding to make the hydrolytic reactivity of silane compound at random to change by the alkoxyl group that contains carbonatoms 3 such as low propoxy-of high methoxy or ethoxy of hydrolytic reactivity and hydrolytic reactivity or butoxy and/or 4 at same molecular.Therefore, be combined with the binder composition of acrylic resin and linking agent and this organopolysiloxane because the amount of the alkoxyl group of hydrolysis is kept necessarily for a long time, so stable performance.

And, because above-mentioned organopolysiloxane has the effect as silane coupling agent, affinity height with glass and acrylic resin, therefore be provided with the blooming of the band tackiness agent of binder layer, when being fitted on the glass substrate with its binder layer side, can suppress becoming flexible, peeling off etc. between binder layer and the glass substrate, described binder layer is formed by the binder composition that has distributed above-mentioned polysiloxane.And find, this organopolysiloxane also presents the effect as the silicon-type stripper, therefore, the re-workability of the blooming of band tackiness agent that is provided with binder layer on being fitted in glass substrate the time is also excellent, described binder layer is formed by the binder composition that is combined with above-mentioned organopolysiloxane, finishes the present invention thus.

Therefore, the invention provides the blooming of following binder composition and band tackiness agent.

(1) a kind of binder composition is characterized in that, contains

(A) acrylic resin,

(B) linking agent and

(C) organopolysiloxane of a following average group accepted way of doing sth (I) expression,

Y _aR ¹ _bSi(OCH ₃) _c(OC ₂H ₅) _d(OR ²) _e(OH) _fO _{(4-a-b-c-d-e-f)/2}......(I)

(in the formula, Y represents to have selected from mercapto, at least a kind organic group in epoxy group(ing), (methyl) acryloxy, thiazolinyl, haloalkyl and the amino;

R ¹The monovalence alkyl of representing the non-replacement of at least a kind of carbonatoms 1～8 that does not have an aliphatics unsaturated link(age);

R ²Alkyl or the methoxy-propyl of representing carbonatoms 3 and/or 4;

A, b, c, d, e and f are for satisfying the number of 0.01≤a≤1,0≤b＜2,0＜c≤2,0≤d≤2,0＜e≤2,0≤f≤1 and 0.1≤c+d+e≤2.5 and 2≤a+b+c+d+e+f≤3.

(2) as (1) described binder composition, wherein, acrylic resin (A) contains following acrylic resin: with the structural unit from (methyl) alkyl acrylate is main component, contains the structural unit from (methyl) acrylic acid series compound with polar functional group.

(3) as (2) described binder composition, wherein, polar functional group is the polar functional group that is selected from free carboxy, hydroxyl, amino and oxirane ring.

(4) as each described binder composition in (1)～(3), wherein, linking agent (B) comprises the isocyanic ester based compound.

(5) as each described binder composition in (1)～(4), wherein, in the above-mentioned average group accepted way of doing sth (I) of expression organopolysiloxane (C), Y is the organic group with sulfydryl or epoxy group(ing).

(6) as each described binder composition in (1)～(5), wherein, in the above-mentioned average group accepted way of doing sth (I) of expression organopolysiloxane (C), b is a positive number, R ¹Be methyl, R ²Be propyl group or sec.-propyl.

(7) as each described binder composition in (1)～(6), wherein, in the above-mentioned average group accepted way of doing sth (I) of expression organopolysiloxane (C), d is a positive number.

(8) as each described binder composition in (1)～(7), wherein, the mean polymerisation degree of organopolysiloxane (C) is 3～100.

(9) a kind of blooming with tackiness agent is characterized in that, at least one face of blooming is provided with the binder layer that is formed by each described binder composition in (1)～(8).

(10) as the blooming of (9) described band tackiness agent, wherein, blooming is selected from polarizing coating and phase retardation film.

(11) as the blooming of (10) described band tackiness agent, wherein, blooming contains pasting at least one face of polaroid and comprises acetyl fibre prime system resin or noncrystalline cyclic polyolefin is the polarizing coating of the protective membrane of resin.

Binder composition of the present invention it is being pasted on blooming, with the state of the blooming of making the band tackiness agent, performance is stable for a long time, even the maximization re-workability is also good in addition, weather resistance is also excellent simultaneously.Therefore, the blooming of this band tackiness agent is preferred for liquid crystal indicator.

Embodiment

Below embodiments of the present invention are elaborated.Binder composition of the present invention must contain following material: (A) acrylic resin, (B) linking agent and (C) organopolysiloxane of an above-mentioned average group accepted way of doing sth (I) expression.At first, these compositions are described.

[acrylic resin]

The acrylic resin that uses among the present invention particularly is preferably following acrylic resin (A-1), be main component promptly, comprise from having free carboxy, hydroxyl, amino, be the monomer of the heterocyclic radical isopolarity functional group of representative with the oxirane ring, preferably have an acrylic resin (A-1) of structural unit of (methyl) acrylic acid series compound of polar functional group with structural unit from (methyl) alkyl acrylate.Here, so-called (methyl) vinylformic acid is meant to be in the acrylic or methacrylic acid any that in addition, " (methyl) " in (methyl) acrylate etc. also is the identical meaning.In addition, the alkyl does not here comprise the alkyl (cycloalkyl) with ester ring type structure.

As (methyl) acrylate, can enumerate: the alkyl acrylate of methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, isobutyl acrylate, ethyl acrylate, Octyl acrylate, Isooctyl acrylate monomer, lauryl acrylate, stearyl acrylate ester, benzyl acrylate, vinylformic acid methoxyl group ethyl ester, vinylformic acid oxyethyl group methyl esters and so on; The alkyl methacrylate of methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid-2-ethylhexyl, Octyl methacrylate, Isooctyl methacrylate, lauryl methacrylate(LMA), methacrylic acid stearyl ester, benzyl methacrylate, methacrylic acid methoxy base ethyl ester, methacrylic acid oxyethyl group methyl esters and so on.These (methyl) alkyl acrylates can be distinguished separately and to use, and also can use different a plurality of their copolymerization that make.

As monomeric example, can enumerate: the monomer with free carboxy of vinylformic acid, methacrylic acid, senecioate-carboxylic ethyl ester and so on polar functional group; The monomer with hydroxyl of (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid-2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-or 3-chloro-2-hydroxypropyl acrylate, Diethylene Glycol list (methyl) acrylate and so on; Acryloyl morpholine, vinyl caprolactone, N-vinyl-2-Pyrrolidone, (methyl) vinylformic acid tetrahydrofuran ester, caprolactone modification vinylformic acid tetrahydrofuran ester, 3,4-epoxycyclohexyl methyl (methyl) acrylate, (methyl) glycidyl acrylate, 2, the monomer with heterocyclic radical of 5-dihydrofuran and so on; N, the monomer with amino different of N-dimethyl aminoethyl (methyl) acrylate and so on etc. with heterocycle.These monomers with polar functional group can be distinguished separately and to use, and also can use different a plurality of.

For the acrylic resin in the binder composition (A-1), in its 100 mass parts, contain structural unit from (methyl) alkyl acrylate with the ratio of common 60～99.9 mass parts, preferred 80～99.6 mass parts, the ratio with common 0.1～20 mass parts, preferred 0.4～10 mass parts contains from the monomeric structural unit with polar functional group in addition.

The acrylic resin that uses among the present invention (A-1) can also contain from except that (methyl) alkyl acrylate of above-mentioned explanation and have monomeric structural unit the monomer of polar functional group.As their example, can enumerate: have the structural unit of (methyl) acrylate of ester ring type structure, have the monomeric structural unit of a plurality of (methyl) acryl etc. from the structural unit of styrenic monomers, from the monomeric structural unit of ethene base system, from intramolecularly from intramolecularly.

So-called ester ring type structure is meant to be generally carbon number 5 or more, the preferred naphthenic hydrocarbon structure of carbon number about 5～7.Object lesson as acrylate with ester ring type structure, can enumerate: isobornyl acrylate, cyclohexyl acrylate, vinylformic acid two rings penta fat, vinylformic acid ring ten diester, vinylformic acid methyl cyclohexane ester, vinylformic acid 3-methyl cyclohexanol ester, vinylformic acid tertiary butyl cyclohexyl, α-ethoxy-c olefin(e) acid cyclohexyl, vinylformic acid cyclohexyl phenyl ester etc., as the object lesson of methacrylic ester, can enumerate: isobornyl methacrylate with ester ring type structure, cyclohexyl methacrylate, methacrylic acid two rings penta fat, methacrylic acid ring ten diester, methyl methacrylate base cyclohexyl, methacrylic acid 3-methyl cyclohexanol ester, methacrylic acid tertiary butyl cyclohexyl, methacrylic acid cyclohexyl phenyl ester etc.

Example as styrenic monomers, except that vinylbenzene, can enumerate: the ring-alkylated styrenes of vinyl toluene, dimethyl styrene, Three methyl Benzene ethene, ethyl styrene, diethylbenzene ethene, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene, octyl group vinylbenzene and so on; The halogenated styrenes of fluorobenzene ethene, chloro-styrene, bromstyrol, Dowspray 9, iodobenzene ethene and so on; And nitrostyrolene, acetylbenzene ethene, methoxy styrene, Vinylstyrene etc.

As the monomeric example of ethene base system, can enumerate: the vinyl fatty ester of vinyl acetate, propionate, vinyl butyrate, 2 ethyl hexanoic acid vinyl acetate, vinyl laurate and so on; The ethylene halide of vinylchlorid, bromine ethene and so on; The halogenation vinylidene chloride of vinylidene chloride and so on; The nitrogenous aromatic vinyl of vinyl pyridine, vinyl pyrrolidone, vinylcarbazole and so on; The conjugate diene monomer of divinyl, isoprene, chloroprene and so on; And vinyl cyanide, methacrylonitrile etc.

The monomeric example that has a plurality of (methyl) acryl as intramolecularly, can enumerate: 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1, the intramolecularly of 9-nonanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, TEG two (methyl) acrylate, tripropylene glycol two (methyl) acrylate and so on has the monomer of 2 (methyl) acryls; The intramolecularly of TriMethylolPropane(TMP) (methyl) acrylate and so on has the monomer of 3 (methyl) acryls etc.

(methyl) acrylate and have monomer beyond the monomer of polar functional group and can distinguish separately and use, or make up more than 2 kinds and use.In the acrylic resin (A-1) that constitutes binder composition, from except that (methyl) acrylate and have monomeric structural unit the monomer of polar functional group in acrylic resin (A-1) 100 mass parts, contain with the ratio of common 0～20 mass parts, preferred 0～10 mass parts.

The effective constituent of binder composition also can contain aforesaid acrylic resin (A-1) more than 2 kinds, and described acrylic resin (A-1) is main component, contains from the monomeric structural unit with polar functional group with the structural unit from (methyl) alkyl acrylate.And, can also in aforesaid propylene acid resin (A-1), be mixed with the acrylic resin different (A-2) with it, described acrylic resin (A-2) is particularly for example for having from the structural unit of (methyl) alkyl acrylate, do not contain the acrylic resin of polar functional group etc., is main component, contains from the acrylic resin (A-1) of the monomeric structural unit with polar functional group and be preferably 60～100 quality % of whole acrylic resins, particularly 80～100 quality % with the structural unit from (methyl) alkyl acrylate.

With the structural unit from (methyl) alkyl acrylate be main component, to contain weight-average molecular weight (Mw) that the polystyrene standard preferably measured by gel permeation chromatography (GPC) from the acrylic resin (A-1) of the monomeric structural unit with polar functional group converts be 1000000～2000000 scope.The weight-average molecular weight that polystyrene standard converts is 1000000 when above, cementability under hot and humid improves, there is the tendency of step-down in the possibility of becoming flexible, peeling off between glass substrate and the binder layer, and the tendency of re-workability existence raising, and is therefore preferred.In addition, this weight-average molecular weight is 2000000 when following, even change owing to pasting the size of the blooming on its binder layer, binder layer also can be followed this dimensional change and be changed, therefore, becoming between the brightness of peripheral part of liquid crystal cell and the brightness of central part does not have difference, and existence can suppress to leak white (Bai order け) and the even tendency of irregular colour, therefore preferred.The molecular weight distribution of ratio (Mw/Mn) expression of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is generally the scope about 2～10.

For acrylic resin (combination is both mixture more than 2 kinds the time), the concentration that it is dissolved in the vinyl acetic monomer and is adjusted to nonvolatile component is the solution of 20 quality %, preferably under 25 ℃, show the viscosity below the 20Pas, more preferably show the viscosity of 0.1～7Pas.The viscosity of this moment is 20Pas when following, and hot and humid cementability down improves, and there is the tendency of step-down in the possibility of becoming flexible, peeling off between glass substrate and the binder layer, and there is the tendency of raising in re-workability, so preferably.Viscosity can be measured by for example Brookfield viscometer.

The acrylic resin (A-1) that constitutes binder composition can be made by for example known the whole bag of tricks such as solution polymerization process, emulsion polymerization, mass polymerization, suspension polymerization.In the manufacturing of this acrylic resin, use polymerization starter usually.Whole monomeric total 100 mass parts of using in the manufacturing with respect to acrylic resin are used the polymerization starter about 0.001～5 mass parts.

As polymerization starter, can use thermal polymerization or Photoepolymerizationinitiater initiater etc.As Photoepolymerizationinitiater initiater, for example can enumerate 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone etc.As thermal polymerization, for example can enumerate: 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexanaphthene-1-nitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2,4-dimethyl-4-methoxyl group valeronitrile), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), 2, the azo based compound of 2 '-azo two (2-hydroxymethyl propionitrile) and so on; Lauroyl peroxide, tert-butyl peroxide, benzoyl peroxide, peroxidized t-butyl perbenzoate, hydrogen peroxide cumene, di-isopropyl peroxydicarbonate, dipropyl peroxydicarbonate, new peroxide tert-butyl caprate, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, (3,5,5-trimethyl acetyl) organo-peroxide of superoxide and so on; The mineral acid superoxide of Potassium Persulphate, ammonium persulphate, hydrogen peroxide and so on etc.In addition, and also can be used as polymerization starter with the redox series initiators of superoxide and reductive agent etc. and use.

As the manufacture method of acrylic resin (A-1), in the method shown in above-mentioned, the preferred solution polymerization.When the object lesson of enumerating solution polymerization process describes, can enumerate and mix desirable monomer and organic solvent, under nitrogen atmosphere, add thermal polymerization, about 40～90 ℃, preferred about 60～80 ℃ methods that stir down about 3～10 hours etc.In addition, in order to control reaction, can in polymerization process, add monomer or thermal polymerization continuously or off and on, or add under the state in being dissolved in organic solvent.Here, as organic solvent, for example can use the aromatic hydrocarbon based of toluene, dimethylbenzene and so on; The ester class of vinyl acetic monomer, N-BUTYL ACETATE and so on; The aliphatics alcohols of propyl alcohol, Virahol and so on; The ketone of methylethylketone, methyl iso-butyl ketone (MIBK) and so on etc.

[linking agent]

In binder composition of the present invention, in above-mentioned acrylic resin, further cooperate linking agent.Linking agent be intramolecularly have at least 2 can with the compound of the crosslinked functional group of polar functional group, specifically for example can enumerate: isocyanic ester based compound, epoxy based compound, metallo-chelate, aziridine based compound etc.

The isocyanic ester based compound is that intramolecularly has at least 2 isocyanate group (compound NCO) for example can be enumerated: tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Xylene Diisocyanate, hydrogenation Xylene Diisocyanate, diphenylmethanediisocyanate, hydrogenation diphenylmethanediisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate etc.In addition, make polyol reaction such as these isocyanate compounds and glycerine or TriMethylolPropane(TMP) and the adducts that obtains, make 2 polymers that isocyanate compound forms, 3 polymers etc. also can be used as the linking agent that uses in the binder composition.Further, can also mix isocyanic ester based compound use more than 2 kinds.

The epoxy based compound is the compound that intramolecularly has at least 2 epoxy group(ing), for example can enumerate: the Resins, epoxy of bisphenol A-type, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, T 55,1,6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, N, N-diglycidylaniline, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (N, N '-diglycidyl amino methyl) hexanaphthenes of 3-etc.Can mix epoxy based compound use more than 2 kinds.

As metallo-chelate, for example can enumerate: coordination has the compound of Acetyl Acetone or methyl aceto acetate etc. on polyvalent metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, barium, chromium and zirconium.

The aziridine based compound is also referred to as ethyleneimine, it is the compound that intramolecularly has the skeleton of at least 23 yuan of rings that comprise 1 nitrogen-atoms and 2 carbon atoms, for example can enumerate: ditan-4,4 '-two (1-aziridine methane amides), Toluene-2,4-diisocyanate, 4-two (1-aziridine methane amide), triethylenemelamine, isophthaloyl is two-1-(2-methylaziridine), three-1-'-aziridino phosphine oxide, hexa-methylene-1,6-two (1-aziridine methane amide), TriMethylolPropane(TMP)-three-β-'-aziridino propionic ester, tetramethylol methane-three-β-'-aziridino propionic ester etc.

In these linking agents, preferably use the isocyanic ester based compound.In addition, and with isocyanic ester based compound and aziridine based compound also is effective.

[organopolysiloxane]

Among the present invention, further cooperate a part to contain the organopolysiloxane of a following average group accepted way of doing sth (I) expression of the organo-functional group multiple alkoxyl group different with carbonatoms.

Y _aR ¹ _bSi(OCH ₃) _c(OC ₂H ₅) _d(OR ²) _e(OH) _fO _{(4-a-b-c-d-e-f)/2}......(I)

In the above-mentioned formula (I), Y is for having the organic group of the functional group in selected from mercapto, epoxy group(ing), (methyl) acryloxy, thiazolinyl, haloalkyl and the amino.In these functional groups, sulfydryl, epoxy group(ing), (methyl) acryloxy and amino Jie usually are bonded on the Siliciumatom by linking group, as this linking group, can enumerate: ehter bond can wherein be arranged, and (O-), imino-(NH-) etc. for example can enumerate: the alkylidene group that comprises methylene radical, ethylidene, trimethylene, hexa-methylene, ten dimethylenes etc. by alkylidene group, the alkylidene group-arylidene-divalent alkyl such as alkylidene group of heteroatomic carbon number 1～12; The divalent alkyl that has aromatic ring in the centre that comprises aminomethyl phenyl ethyl etc.; Comprise the divalent aliphatic group that has Sauerstoffatom in the centre of methoxymethyl, methoxy ethyl, methoxy-propyl etc. etc.Thiazolinyl and haloalkyl can be situated between and be bonded on the Siliciumatom by above-mentioned linking group, also can Direct Bonding on Siliciumatom.

When enumerating the object lesson of the organic group with functional group (the following group of sometimes Y being represented is called " organo-functional group ") that Y represents, as organic group with sulfydryl, but illustration: mercapto methyl, 3-sulfydryl propyl group, 6-sulfydryl hexyl, 10-sulfydryl decyl, 2-(4-mercapto methyl phenyl) ethyl etc., as organic group with epoxy group(ing), but illustration: glycidoxypropyl methyl, the 3-glycidoxypropyl, 5,6-epoxy group(ing) hexyl, 9,10-epoxy group(ing) decyl, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl, 2-(3,4-epoxy group(ing)-4-methylcyclohexyl) propyl group etc., as organic group with (methyl) acryloxy, but illustration: acryloyl-oxy ylmethyl, 3-acryloxy propyl group, 6-acryloxy hexyl, 10-acryloxy decyl, the methacryloxy methyl, the 3-methacryloxypropyl, 6-methacryloxy hexyl, 10-methacryloxy decyl etc., as organic group with thiazolinyl, but illustration: vinyl, allyl group, the 5-hexenyl, 9-decene base, 3-vinyl oxygen base propyl group, to styryl, cyclohexenyl ethyl etc., as organic group with haloalkyl, but illustration: chloromethyl, the 3-chloropropyl, 6-chlorine hexyl, 10-chlorine decyl, brooethyl, 3-bromopropyl etc., as having amino organic group, but illustration: amino methyl, the 3-aminopropyl, the amino hexyl of 6-, N-methyl-3-aminopropyl, N, N-dimethyl-3-aminopropyl, N-phenyl-3-aminopropyl, N-(2-amino-ethyl)-3-aminopropyl, N-(the amino hexyl of 6-)-3-aminopropyl, N-(vinyl benzyl)-2-amino-ethyl-3-aminopropyl etc.

In the organopolysiloxane that the present invention uses, in above-mentioned organo-functional group, be set at have sulfydryl, during the organic group of epoxy group(ing) or (methyl) acryloxy, reactive high because of it, so it is preferred, especially the organic group that has sulfydryl or epoxy group(ing), the effect height of the bonding force of increase glass and blooming, therefore more preferably.

In addition, in above-mentioned formula (I), R ¹Monovalence alkyl for the non-replacement of at least a kind of carbonatoms 1～8 that does not have an aliphatics unsaturated link(age), particularly, but illustration: alkyl such as methyl, ethyl, propyl group, sec.-propyl, 1-methyl-propyl, butyl, isobutyl-, the tertiary butyl, hexyl, octyl group, phenyl, tolyl, benzyl, phenylethyl; Aryl; Aralkyl, if desired, as R ¹Also can import a plurality of groups.Wherein, consider from sterically hindered reactive influence and cost aspect, especially preferably with R above-mentioned organo-functional group ¹Be set at methyl.

In above-mentioned formula (I), R ²Be the alkyl of carbonatoms 3 and/or 4, particularly, can be propyl group, sec.-propyl, 1-methyl-propyl, butyl, isobutyl-or the tertiary butyl.In addition, methoxy-propyl is also contained in R as the group that can obtain identical effect ²In.If desired, as R ²Also can import a plurality of groups.Wherein, from the aspect that hydrolytic reactivity is suitably reduced, the volume size of alkyl the viewpoint of the influence of the content (equivalent) of above-mentioned organo-functional group is considered, especially preferably with R ²Be set at propyl group or sec.-propyl.

Further, in above-mentioned formula (I), a, b, c, d, e and f are for satisfying the number of 0.01≤a≤1,0≤b＜2,0＜c≤2,0≤d≤2,0＜e≤2,0≤f≤1 and 0.1≤c+d+e≤2.5 and 2≤a+b+c+d+e+f≤3.

Here, coefficient a is the numerical value of expression organo-functional group to the substitution value of Siliciumatom, if this numerical value is too small, when then using organopolysiloxane, can not bring into play the originally due characteristic that produces by the reactivity of organo-functional group, need in a part, have an organo-functional group at least, on the other hand, because there was difficulty greater than 1 o'clock in the substitution value that makes organo-functional group aspect synthetic method and the cost, therefore be set at the scope of 0.01≤a≤1.Be preferably the scope of 0.1≤a≤1, more preferably the scope of 0.1≤a≤0.8.

Coefficient b represents not have the monovalence alkyl of non-replacement of carbonatoms 1～8 of aliphatics unsaturated link(age) to the numerical value of the substitution value of Siliciumatom, this numerical value is 0 or approached 0 o'clock, the content of alkoxyl group increases relatively, contribution rate to hydrolysis reaction, silylation reactive uprises, depend on situation, organopolysiloxane increases the affinity of water.On the other hand, when this numerical value is big, the kind that depends on the monovalence alkyl, has the cured article giving the consistency (phenyl etc.) of organopolysiloxane, give tackiness agent with flexibility, release property effects such as (methyl) with hydrophobicity (alkyl etc.), raising and acrylic resin, when b becomes big, because the content of alkoxyl group reduces relatively, therefore, is not suitable for making full use of reactive adhesive applications of alkoxysilyl.Therefore, according to application target, be set at the scope of 0≤b＜2.Be preferably the scope of 0≤b≤1, more preferably the scope of 0≤b≤0.8.

Coefficient c, d and e are the numerical value of the different multiple alkoxyl group of expression carbonatoms to the substitution value of Siliciumatom, and c represents the substitution value of methoxyl group, and d represents the substitution value of oxyethyl group, and e represents the substitution value of the alkoxyl group of carbonatoms 3 and/or 4.The c and the d of the methoxyl group that the expression hydrolytic reactivity is high and the containing ratio of oxyethyl group, e with the containing ratio of the alkoxyl group of the carbonatoms 3 of low propoxy-of expression hydrolytic reactivity or butoxy etc. and/or 4, can be according to application target separately, the degree of desirable hydrolytic reactivity is suitably set, considering from the such purpose of the present invention that has the different multiple alkoxyl group of hydrolytic reactivity same molecular, is 0＜c≤2, the scope of 0≤d≤2, the scope of 0＜e≤2, and the c+d+e of the total substitution value of expression alkoxyl group is set at the scope of 0.1≤c+d+e≤2.5.Be preferably among 0＜c≤1.8,0＜d≤1.8, c and the d at least one and be more than 0.1, the scope of 0.1≤e≤1.8,0.2≤c+d+e≤2.35, the more preferably scope of 0.1≤c≤1.8,0.1≤d≤1.8,0.1≤e≤1.8,0.5≤c+d+e≤2.35.Consider from the reactive viewpoint of control hydrolysis suitably, preferably contain these two groups of methoxyl group and oxyethyl group and further contain the organopolysiloxane of the alkoxyl group of carbonatoms 3 and/or 4.

In addition, coefficient f be the expression hydroxyl to the substitution value of Siliciumatom, be the numerical value of the containing ratio of silanol group, this silanol group can keep in silylation reactive and condensation reaction, has the organopolysiloxane of giving with hydrophilic effect, consider from the viewpoint of the storage stability of guaranteeing organopolysiloxane, preferably the least possible.Therefore, be set at the scope of 0≤f≤1.Be preferably the scope of 0≤f≤0.5, more preferably the scope of 0≤f≤0.2.

The total a+b+c+d+e+f of above-mentioned each coefficient is the numerical value of [4-(a+b+c+d+e+f)]/2 of the decision table condensation degree that is shown with the machine polysiloxane, is set at the scope of 2≤a+b+c+d+e+f≤3.It is that 2 dipolymer is the scope of the polymkeric substance about hundreds of to Siliciumatom that the polymerization degree of this organopolysiloxane can be set at from Siliciumatom, mean polymerisation degree is 2 o'clock, it is many that monomer content in the organopolysiloxane that makes becomes, organosilicon alcoxyl base oligopolymer application target originally is impaired, when mean polymerisation degree is excessive, become high-viscosity material or pasty state or solid state, it is difficult to handle change, therefore preferably mean polymerisation degree is set in 3～100 scope, more preferably is set in 3～50 scope.From the viewpoint, about above-mentioned a+b+c+d+e+f, be preferably the scope of 2≤a+b+c+d+e+f≤2.67, more preferably the scope of 2＜a+b+c+d+e+f≤2.67.

A part of the present invention contains the organopolysiloxane of the organo-functional group multiple alkoxyl group different with carbonatoms and represents with an above-mentioned average group accepted way of doing sth (I), a～f is respectively the number that satisfies above-mentioned scope and gets final product, the structure that also can have straight chain shape, a chain, ring texture and their combinations are obtained.

[manufacture method of organopolysiloxane]

A part contains the organopolysiloxane of the organo-functional group multiple alkoxyl group different with carbonatoms and can make by known various method for making in the past, as general method, for example can enumerate following method.

(1) make the above-mentioned organoalkoxysilane that contains the organo-functional group multiple alkoxyl group different with carbonatoms carry out separately the method for partial hydrolysis polycondensation,

(2) organoalkoxysilane that does not contain organo-functional group that makes the organoalkoxysilane that contains organo-functional group and contain the carbonatoms alkoxyl group different with it carry out the polycondensation of part cohydrolysis method,

(3) by with the transesterification reaction of the alcohol of carbonatoms 3 and/or 4, by same partial hydrolysis. import the method etc. of the alkoxyl group of carbonatoms 3 and/or 4 in the organopolysiloxane that contains organo-functional group and methoxyl group and/or oxyethyl group that the polycondensation operation obtains.

In the present invention, consider from the viewpoint of the degree of freedom of the structure design of organopolysiloxane, easiness that raw material obtains, preferably according to the method for making of above-mentioned (2), make at least a following general formula (II) expression the organoalkoxysilane that contains organo-functional group and/or its partial hydrolysate, carry out part cohydrolysis and polycondensation with the silane compound that contains alkoxyl group of at least a following general formula (III) expression and/or the mixture of its partial hydrolysate and/or its condenses, form organopolysiloxane.

YR ¹ _mSi(OCH ₃) _n(OC ₂H ₅) _3-m-n ......(II)

R ¹ _pSi(OCH ₃) _q(OC ₂H ₅) _r(OR ²) _4-p-q-r ......(III)

Here, Y, R ¹And R ²Respectively the expression with above-mentioned formula (I) in the identical meaning, m is 0～2 integer, n is 0～3 integer, and m+n is below 3, and p is 0～2 integer, q is 0～4 integer, r is 0～4 integer, and p+q+r is below 4, wherein, as the n of general formula (II) and/or the q of general formula (III), use at least a OCH that has ₃The composition of base as the silane compound that contains alkoxyl group of general formula (III), uses at least a OR that has simultaneously ²The composition of group.

In addition, as deformation method, can also form organopolysiloxane by the following method.That is, at first, make the organoalkoxysilane that contains organo-functional group of above-mentioned general formula (II) expression and at least a silane compound that contains alkoxyl group of above-mentioned general formula (III) expression carry out cohydrolysis in advance.Then, mix with the employed different silane compound that contains alkoxyl group and/or its partial hydrolysate and/or its condenses in the part cohydrolysis before this part cohydrolysis resultant and above-mentioned general formula (III) are expression, make them carry out partial hydrolysis and polycondensation, obtain organopolysiloxane.In this method,, be set at and use at least a OR of having as the silane compound that contains alkoxyl group of above-mentioned general formula (III) expression ²The composition of group.

When enumerating the object lesson of the organoalkoxysilane that contains organo-functional group of above-mentioned general formula (II) expression, but illustration: have mercapto methyl, 3-sulfydryl propyl group, 6-sulfydryl hexyl, 10-sulfydryl dodecyl, 2-(4-mercapto methyl phenyl) ethyl, the glycidoxypropyl methyl, the 3-glycidoxypropyl, 5,6-epoxy group(ing) hexyl, 9,10-epoxy group(ing) decyl, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl, 2-(3,4-epoxy group(ing)-4-methylcyclohexyl) propyl group, the acryloyl-oxy ylmethyl, 3-acryloxy propyl group, 6-acryloxy hexyl, 10-acryloxy decyl, the methacryloxy methyl, the 3-methacryloxypropyl, 6-methacryloxy hexyl, 10-methacryloxy decyl, vinyl, allyl group, the 5-hexenyl, 9-decene base, 3-vinyl oxygen base propyl group, to styryl, the cyclohexenyl ethyl, chloromethyl, the 3-chloropropyl, 6-chlorine hexyl, 10-chlorine decyl, brooethyl, the 3-bromopropyl, amino methyl, the 3-aminopropyl, the 6-aminopropyl, N-methyl-3-aminopropyl, N, N-dimethyl-3-aminopropyl, N-phenyl-3-aminopropyl, N-(2-amino-ethyl)-3-aminopropyl, N-(the amino hexyl of 6-)-3-aminopropyl, N-(vinyl benzyl)-2-amino-ethyl-3-aminopropyls etc. are as the Trimethoxy silane compound of organo-functional group, the triethoxysilicane hydride compounds, the methyl dimethoxysilane compound, the methyldiethoxysilane compound, ethyl dimethoxy silane compound, ethyl diethoxy silane compound, propyl group dimethoxy silane compound, propyl group diethoxy silane compound, dimethyl methyl TMOS compound, the dimethylethoxysilane compound, oxyethyl group dimethoxy silane compound, methoxyl group diethoxy silane compound etc.

Below, when enumerating the object lesson of the silane compound that contains alkoxyl group of above-mentioned general formula (III) expression, as the organoalkoxysilane of p=0, but illustration: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, tetraisobutoxy-silicane alkane etc.; As the organoalkoxysilane of p=1, but illustration: have Trimethoxy silane, triethoxyl silane, tripropoxy silane, three isopropoxy silane, three butoxy silanes, three isobutoxy silane of methyl, ethyl, propyl group, sec.-propyl, 1-methyl-propyl, butyl, isobutyl-, the tertiary butyl, hexyl, octyl group, phenyl, tolyl, benzyl, phenylethyl etc. etc.; As the organoalkoxysilane of p=2, but illustration: dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl dipropoxy silane, dimethyl dibutoxy silane, methylethyl dimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane etc.

What illustrated is, consider from the acquisition easiness of raw material, cost aspect, use preferably that m in the above-mentioned general formula (II) is 0, n is 3 or 0 compound, promptly contain Trimethoxy silane, triethoxyl silane and/or its partial hydrolysate of organo-functional group and the R in the above-mentioned general formula (III) ¹For methyl, p are that 1 and/or 0 compound is methyl trialkoxysilane, tetraalkoxysilane and/or its partial hydrolysate and/or its condenses, all be that 0 the silane compound that contains alkoxyl group and/or its partial hydrolysate and/or its condenses are as neccessary composition more preferably with q in the above-mentioned general formula (III) and r.

Especially, preferred especially the use is selected from 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxy group(ing) cyclohexyl) at least a organoalkoxysilane that contains organo-functional group in the ethyl triethoxysilane as above-mentioned general formula (II) expression, use is selected from methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three isopropoxy silane, methyl three butoxy silanes, methyl three isobutoxy silane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, at least a in the tetraisobutoxy-silicane alkane (wherein, has a propoxy-with at least a, isopropoxy, the silane compound of butoxy or isobutoxy is as neccessary composition) as the silane compound that contains alkoxyl group of above-mentioned general formula (III) expression.

These contain organoalkoxysilane and/or its partial hydrolysate of organo-functional group and contain the silane compound of alkoxyl group and/or its partial hydrolysate and/or its condenses respectively can and with multiple, but when using the organoalkoxysilane that contains organo-functional group of two or more above-mentioned general formulas (II) expressions and/or its partial hydrolysate, preferably has identical organo-functional group.In addition, for the ratio of the alkoxyl group that at random designs methoxyl group in the organopolysiloxane, oxyethyl group, carbonatoms 3 and/or 4, preferred and with the diverse two or more silane compound that contains alkoxyl group and/or its partial hydrolysate and/or its condensess of representing as above-mentioned general formula (III) of alkoxyl group.

The organoalkoxysilane that contains organo-functional group and/or its partial hydrolysate of above-mentioned general formula (II) expression, be not particularly limited with the silane compound that contains alkoxyl group of above-mentioned general formula (III) expression and/or the cooperation ratio of its partial hydrolysate and/or its condenses, when the former cooperation ratio is very few, when using resultant organopolysiloxane, reactive characteristic based on the due organo-functional group of script can not be given full play to, need to have an organo-functional group at least one molecule, therefore, preferably be 1: 99～99: 1 scope with the Si atom conversion molar ratio computing of two compositions, more preferably 10: 90～80: 20 scope.

In addition, the cooperation order of these various raw materials, blending means, and carry out the part cohydrolysis, the method of polycondensation also is not particularly limited, can be according to known method in the past, for example, can be by at above-mentioned organoalkoxysilane and/or its partial hydrolysate that contains organo-functional group, in the mixture of the silane compound that contains alkoxyl group and/or its partial hydrolysate and/or its condenses, add water to carry out part cohydrolysis and polycondensation in the presence of the hydrolysis-condensation reaction catalyzer and obtain, also can use suitable organic solvent as required this moment.

Hydrolysis-condensation reaction catalyzer as in this reaction can use known in the past various catalyzer.As object lesson, can enumerate: organic acids such as acetic acid, trifluoracetic acid, butyric acid, oxalic acid, toxilic acid, citric acid, methanesulfonic, tosic acid, trifluoromethayl sulfonic acid; Inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid; Basic cpd classes such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, yellow soda ash, sodium-acetate, Potassium ethanoate, ammonia, ammonium hydroxide, triethylamine; Fluorochemicals such as Potassium monofluoride, Neutral ammonium fluoride class; Organometallic compound classes such as phthalandione four isopropyl esters, phthalandione four butyl esters, dioctyl tin dilaurate, aluminum chelate class etc.Above-mentioned catalyzer can use separately, also can and with multiple, the usage quantity of catalyzer preferably with respect to being present in the scope that Si atomic molar number in whole raw materials is set at 0.0001～10 mole of %, more preferably is set at the scope of 0.001～3 mole of %.

As mentioned above, the polymerization degree of organopolysiloxane is for being that 2 dipolymer is that polymkeric substance about hundreds of gets final product to Siliciumatom from Siliciumatom, decides mean polymerisation degree according to the amount of the water that uses in partial hydrolysis, the polycondensation.When adding water, the alkoxyl group hydrolysis of its part becomes the many resinites of branched structure, can not get the organosilicon alcoxyl base oligopolymer of target superfluously, and therefore, the amount of the water that uses in the hydrolysis needs decision modestly.For example, when employed organoalkoxysilane raw material is 1 a monomer for Siliciumatom entirely, prepare the organopolysiloxane of mean polymerisation degree Z, use with respect to the organoalkoxysilane raw material of Z mole that the water of (Z-1) mole carries out partial hydrolysis, polycondensation gets final product.

At this moment, also can use organic solvents such as alcohols, ethers, ester class, ketone as required.As the object lesson of these organic solvents, can enumerate: alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propylene glycol monomethyl ether; Ethers such as diethyl ether, dipropyl ether; Ester classes such as ritalin, vinyl acetic monomer, methyl aceto acetate; Ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) etc.In addition, can together also use non-polar solvents such as hexane, toluene, dimethylbenzene with aforesaid polar solvent.Especially preferably use alcohols such as methyl alcohol, ethanol, Virahol.

The usage quantity of organic solvent gets final product with respect to the scope that total 100 mass parts as the organoalkoxysilane of raw material and/or its partial hydrolysate and/or its condenses are set at 0～1000 mass parts, but usage quantity after a little while, it is even that reaction system when hydrolysis begins can not become sometimes, in the time of too much, not only can not obtain its above additive effect, and pot yield reduces, be disadvantageous economically, therefore, be preferably set to the scope of 10～500 mass parts, more preferably be set at the scope of 20～200 mass parts.

As the actually operating in part (being total to) hydrolysis and the polycondensation, preferably in the mixed system that comprises organoalkoxysilane raw material, catalyzer and organic solvent, drip the water of specified amount or the mixed solution of water/organic solvent, or in the mixed system that comprises organoalkoxysilane raw material and organic solvent, drip the mixing solutions of water/catalyzer of specified amount or the mixing solutions of water/catalyzer/organic solvent.At this moment, also can make organoalkoxysilane raw material in advance respectively and have the organoalkoxysilane raw material partial hydrolysis of the alkoxyl group of carbonatoms 3 such as low propoxy-of hydrolytic reactivity or butoxy and/or 4 with the high methoxy or ethoxy of hydrolytic reactivity, then two compositions are mixed, according to circumstances carry out the part cohydrolysis again, carry out polycondensation then.Also can carry out each reaction 0～150 ℃ temperature range, but usually, when under the temperature lower, reacting than room temperature, carrying out of reaction is slack-off, therefore impracticable, in addition, when under too high temperature, reacting, detrimentally affect to organo-functional group such as the thermolysis of sulfydryl, epoxy group(ing) etc. or the thermopolymerization of acryloxy takes place, and therefore is preferably set to 20～130 ℃ temperature range.After the reaction, carry out removing the refining step that distillations such as the operation of employed catalyzer, the alcohol that adopts employed organic solvent and by-product life, low-boiling point material are removed, can obtain the organopolysiloxane of target by neutralization, absorption, filtration etc.The organopolysiloxane that obtains thus in most cases is liquid.

[binder composition]

Among the present invention, same above-mentioned illustrated linking agent and the organopolysiloxane of cooperating forms binder composition in as above illustrated acrylic resin.Linking agent with respect to acrylic resin 100 mass parts that constitute binder composition (when using more than 2 kinds be its total amount) usually with about 0.1～10 mass parts, about preferred 0.1～7 mass parts, the more preferably cooperation of the ratio about 0.2～3 mass parts.With respect to the amount of the linking agent of acrylic resin 100 mass parts is 0.1 mass parts when above, and there is the tendency that improves in the weather resistance of binder layer, and is therefore preferred.In addition, its amount is 10 mass parts when following, and the so-called leakage leucismus the when blooming of band tackiness agent is used for liquid crystal indicator gets not obvious, therefore preferred.

Organopolysiloxane with respect to acrylic resin 100 mass parts that constitute binder composition (when using more than 2 kinds be its total amount) usually with about about 0.0001～10 mass parts, about preferred 0.01～5 mass parts, the more preferably use of the ratio about 0.1～1 mass parts.With respect to the amount of the organopolysiloxane of acrylic resin 100 mass parts is 0.0001 mass parts when above, and the adaptation of binder layer and glass substrate improves, and is therefore preferred.In addition, its amount is 10 mass parts when following, exists and suppresses the tendency that organopolysiloxane oozes out from binder layer, and is therefore preferred.

In the binder composition of above explanation, can also cooperate crosslinking catalyst, weather-proof stablizer, tackifier, softening agent, tenderizer, dyestuff, pigment, mineral filler etc.Wherein, when in tackiness agent, cooperating crosslinking catalyst with linking agent, can prepare binder layer by the slaking of short period of time, be fitted in liquid crystal cell when on glass at the blooming of the band tackiness agent that will obtain, can suppress to become flexible, peel off or in bonding coat, bubble between binder layer and the blooming, and re-workability also becomes better sometimes.As crosslinking catalyst, for example can enumerate: the amine compound of hexamethylene-diamine, quadrol, polymine, vulkacit H, diethylenetriamine, Triethylenetetramine (TETA), isophorone diamine, trimethylene diamines, poly-aminoresin, melamine resin and so on etc.When the complex amine based compound is as crosslinking catalyst in tackiness agent, as linking agent, the preferred isocyanate based compound.

Binder composition is prepared with the state that aforesaid each composition is dissolved in the organic solvent usually.The organic solvent that is used for this purposes is that the organic solvent of above-mentioned each composition of dissolving gets final product, and for example can use the aromatic hydrocarbon based of toluene, dimethylbenzene and so on, the ester class of vinyl acetic monomer, N-BUTYL ACETATE and so on, the ketone of acetone, methylethylketone, methyl iso-butyl ketone (MIBK) and so on etc.

[blooming of band tackiness agent]

The blooming of band tackiness agent of the present invention is the blooming that at least one face of blooming is provided with the binder layer that is formed by above binder composition.Blooming used herein is meant the film with optical characteristics, for example can enumerate: polarizing coating, phase retardation film etc.

Polarizing coating is meant to have the blooming that penetrates the function of polarized light for the incident light of natural light etc.For polarizing coating, following polarizing coating etc. is arranged: possess the rectilinearly polarized light that absorbs vibration plane, see through the straight line polarizing coating of the character of rectilinearly polarized light with perpendicular crossing vibration plane with a certain direction; Possess rectilinearly polarized light that reflection has the vibration plane of a certain direction, and see through the polarization separating film of the character of rectilinearly polarized light with perpendicular crossing vibration plane; The laminated elliptical polarization film that polarizing coating and phase retardation film described later are arranged etc.As the polarizing coating preferred object lesson of straight line polarizing coating (being sometimes referred to as polaroid or polarizer membrane) particularly, can enumerate: the absorption orientation has the polarizing coating of dichroism pigments such as iodine or dichroic dye on the polyvinyl alcohol resin film of uniaxial extension.

Phase retardation film is meant and shows optically anisotropic blooming, for example can enumerate: by the polymeric membrane that will comprise polyvinyl alcohol, polycarbonate, polyester, polyarylester, polyimide, polyolefine, cyclic polyolefin, polystyrene, polysulfones, polyethersulfone, polyvinylidene difluoride (PVDF)/polymethylmethacrylate, liquid crystal polyester, cellulose acetate, ethylene-vinyl acetate copolymer saponated material, polyvinyl chloride etc. about 1.01～6 times stretched film that obtain etc. that stretch.Wherein, preferably polycarbonate membrane or cyclic polyolefin mesentery are carried out uniaxial extension or biaxial stretch-formed polymeric membrane.Be called as the film of uniaxiality phase retardation film, wide-angle phase retardation film, low light Young's modulus phase retardation film etc. in addition, to its its any, all applicable.

In addition, the coating orientation by liquid crystal compounds presents the film that the film of each diversity of optics and the coating by inorganic layered compounds present each diversity of optics and also can be used as phase retardation film.For such phase retardation film, the film that is called as the temperature compensating type phase retardation film is arranged, reverse the film of orientation in addition from the rod shaped liquid crystal with trade(brand)name " LC film " sale of Shin Nihon Oil Co., Ltd, equally from the film of the rod shaped liquid crystal inclination orientation of selling with trade(brand)name " NH film " of Shin Nihon Oil Co., Ltd, film from the discoid liquid crystal inclination orientation of selling with trade(brand)name " WV film " of the Off イ of Fuji Le system Co., Ltd., film from the complete twin shaft alignment-type of selling with trade(brand)name " VAC film " of Sumitomo Chemical Co, equally from the film of the twin shaft alignment-type of selling with trade(brand)name " new VAC film " of Sumitomo Chemical Co etc.

And the film that is pasting protective membrane on these bloomings also can be used as blooming.As protective membrane; can use transparent resin molding; as this transparent resin, for example can enumerate: the acetyl fibre prime system resin of triacetyl cellulose, diacetyl cellulose representative, the noncrystalline cyclic polyolefin of norbornene resin representative is a resin; the methacrylic resin of polymethylmethacrylate representative; vibrin, polyolefin resin, polycarbonate resin; polyether-ether-ketone resin, polysulfone resin etc.In the resin that constitutes protective membrane, can also cooperate UV light absorber such as salicylate based compound, benzophenone based compound, benzotriazole based compound, triazine based compound, cyanoacrylate based compound, nickel complexing salt based compound.As protective membrane, preferably use noncrystalline cyclic polyolefin resin films such as cellulose acetate resin film, norbornene resin film such as tri acetyl cellulose membrane.Commercially available product as the noncrystalline cyclic polyolefin resin film for example has: " the ア one ト Application Off イ Le system " sold by JSR Corp., (being trade(brand)name) such as " ゼ オ ノ ア Off イ Le system " of being sold by オ プ テ ス Co., Ltd..In addition, can also use above-mentioned phase retardation film as direct protective membrane.

In the blooming of above-mentioned explanation, the many state uses of pasting protective membrane with the one or both sides that for example comprise the polarizer membrane of polyvinyl alcohol resin at the polaroid that constitutes it of straight line polarizing coating.In addition, above-mentioned elliptical polarization film is the laminated polarizing coating that straight line polarizing coating and phase retardation film are arranged, and this straight line polarizing coating also mostly is the state that is pasting protective membrane at the one or both sides of polarizer membrane.When on such elliptical polarization film, forming binder layer of the present invention, form binder layer in its phase retardation film side usually.As the preferred example that is provided with the blooming of binder layer according to the present invention, can enumerate: contain on the one side at least of polaroid, pasting and comprise the blooming of polarizing coating that acetyl fibre prime system resin or noncrystalline cyclic polyolefin are the protective membrane of resin.

The blooming of band tackiness agent can wait by for example following method to be made, and described method is: the binder composition of the above-mentioned explanation of coating forms binder layer on stripping film, again the method for laminated optical film on the binder layer that obtains; Applying adhesive composition on blooming and form binder layer is protected at its tackiness agent face applying stripping film, forms the method etc. of the blooming of band tackiness agent.Here, as stripping film, for example can enumerate: with the film that comprises various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylester as base material, to implementing that the demoulding that organosilicon handles and so on is handled and the stripping film that obtains etc. with the junction surface of the binder layer of this base material.Binder layer can be by being coated in foregoing binder composition as organic solvent solution on above-mentioned stripping film or the blooming, carrying out the exsiccant method and form.Coating can be used known various coating machine.After the coating, usually in slaking under the relative humidity about the temperature about 0～50 ℃ and 20～80% about 3～14 days.The preferred condition of slaking is: temperature is about 20～30 ℃, relative humidity is about 55～75%, the time is about 5～7 days.By this slaking, promote the crosslinking reaction of tackiness agent.When being arranged on binder layer on the stripping film, slaking can be formed with binder layer on this stripping film state carries out, and also can carry out after being laminated in the binder layer on the stripping film on the blooming.

The thickness of binder layer is not particularly limited, and is preferably usually below the 30 μ m, and is preferably more than the 10 μ m.The thickness of binder layer is that 30 μ m are when following, cementability under hot and humid improves, possibility loosening and that peel off takes place between glass substrate and binder layer the tendency that reduces, and, there is the tendency that improves in re-workability, therefore preferred, in addition, its thickness is that 10 μ m are when above, the size of blooming there changes, binder layer is also followed its dimensional change and changed even be fitted in, therefore do not have difference between the brightness of brightness of peripheral part of liquid crystal cell and central part, have the tendency that suppresses to leak white and irregular colour, therefore preferred.

The blooming of band tackiness agent of the present invention can be on its binder layer the laminated glass substrate, form optical laminate.Here, as glass substrate, for example can enumerate: the glass substrate of liquid crystal cell, anti-dazzle with glass, sun glasses with glass etc.Wherein, the optical laminate that laminated other the blooming (following polarizing coating) of band tackiness agent forms on the blooming (going up polarizing coating) of the glass substrate upper strata crossed belt tackiness agent of the front face side (viewable side) of liquid crystal cell, glass substrate in the rear side of liquid crystal cell can be used as liquid crystal indicator and uses.As the material of glass substrate, for example can enumerate: soda-lime glass, glass with lower alkali content, non-alkali glass etc.In order will to be combined in the optical film of tackiness agent on the glass substrate, form optical laminate, for example, peel stripping film from the blooming of the above-mentioned band tackiness agent that obtains, the surface that the binder layer that will expose is fitted in glass substrate gets final product.

The blooming of band tackiness agent of the present invention is being peeled off on the substrate and after forming optical laminate pasting, if some is improper with this blooming when glass substrate is peeled off, binder layer is accompanied by blooming and is stripped from together, bluring, sticking with paste residual etc. hardly with the surface of the contacted glass substrate of binder layer, the blooming that therefore heavily pastes the band tackiness agent on the glass substrate after peeling off once more is easy.That is so-called re-workability excellence.

The one side at least that the blooming of band tackiness agent of the present invention is fitted in liquid crystal cell glass goes up and the liquid crystal indicator that forms can be used for for example comprising the Personal Computer liquid-crystal display, TV, vehicle mounted indicating meter, electronic dictionary, digital camera, Digital Video, electronic calculator, clock and watch of notebook type, desktop type, PDA (Personal Digital Assistance) etc. etc.

Embodiment

Below enumerate embodiment the present invention is carried out more specific description, but the present invention is not limited to these examples.In the example, the part and the % of expression usage quantity and even content if not otherwise specified, are quality criteria just.

In the following example, the nonvolatile component of acrylic resin be use based on the method for JIS K 5407 measure value.Particularly, be with the binder solution of getting any quality in dish and in explosion-proof stove in 115 ℃ of values of representing of quality and the ratio of the quality of the initial solution of measuring of the residual nonvolatile component after dry 2 hours down.The weight-average molecular weight of acrylic resin is connected in the GPC device and is linked manufacturing " the TSK gelGMH of configuration 2 Gen East ソ one Co., Ltd. _HR-H (S) " as pillar, use tetrahydrofuran (THF) as elutriant, the condition at sample solution concentration 5mg/ml, sample import volume 100 μ l, 40 ℃ of temperature, flow velocity 1ml/ minute converts by polystyrene standard and measures the value that gets.

In addition, the analysis of the organopolysiloxane that is obtained by each example is carried out according to method shown below.

(1) molecular-weight average of organopolysiloxane and mean polymerisation degree

Analyzing by gel permeation chromatography (GPC), is benchmark with the typical curve that is made by the polystyrene standard sample, obtains weight-average molecular weight, calculates mean polymerisation degree by it again.

(2) alkoxy group content in the organopolysiloxane

Utilize base catalysis cracking (alkali cracking)-gas-chromatography (GC) analytical method [with reference to 792～793 pages of (nineteen nineties of organosilicon handbook, Nikkan Kogyo Shimbun's distribution)], measure alkoxy group content, determine coefficient c and d and e in the above-mentioned average group accepted way of doing sth (I).

(3) structure elucidation of organopolysiloxane

By the silicon NMR (Nuclear Magnetic Resonance) spectrum ( ²⁹Si-NMR) analyze and proton nuclear magnetic resonance spectroscopy ( ¹H-NMR) analyze and carry out, determine coefficient a, b and f in the above-mentioned average group accepted way of doing sth (I) by measurement result.

(4) the sulfydryl equivalent of organopolysiloxane

Measure according to acetic acid/potassiumiodide/Potassium Iodate interpolation-sodium thiosulfate solution titrated method [, revising 432～433 pages of second editions (1976, the distribution of the kind Co., Ltd. of ball)] with reference to the analytical chemistry brief guide.

(5) viscosity of organopolysiloxane

By the viscosity under measuring 25 ℃ based on the method for JIS K 8803.

At first, express the example of the acrylic resin of making the present invention's use.

[polymerization example 1]

The mixed solution that in reactor, adds 1.1 parts in 81.8 parts of vinyl acetic monomers, 98.9 parts of butyl acrylates and vinylformic acid with cooling tube, nitrogen ingress pipe, thermometer and stirrer, with the air in the nitrogen replaceable equipment, form oxygen-free gas, make internal temperature rise to 55 ℃ simultaneously.Add the solution that vinyl acetic monomer 10 part are dissolved with Diisopropyl azodicarboxylate (polymerization starter) 0.14 part of all thereafter.Add initiator after 1 hour, in reactor, add vinyl acetic monomer continuously for 17.3 parts/hour with interpolation speed, so that the concentration of the acrylic resin outside the demonomerization becomes 35%, simultaneously, be incubated 12 hours down for 54～56 ℃ at internal temperature, add vinyl acetic monomer at last, with the concentration adjustment to 20% of acrylic resin.The acrylic resin that obtains is 1670000 by the weight-average molecular weight Mw of the polystyrene conversion that GPC measures, and Mw/Mn is 4.4.With it as acrylic resin A1.

[polymerization example 2]

Monomer formed be transformed to 0.2 part in 98.8 parts of butyl acrylates, vinylformic acid-1.0 parts of 2-hydroxyl ethyl esters and vinylformic acid, same with polymerization example 1 in addition, obtain acrylic resin soln.The acrylic resin that obtains is 1470000 by the weight-average molecular weight Mw of the polystyrene conversion that GPC measures, and Mw/Mn is 4.2.With it as acrylic resin A2.

Express the example of the organopolysiloxane of synthetic the present invention's use below.

[organopolysiloxane synthesis example 1]

In the flask of the capacity 1L that whipping appts, cooler condenser, thermometer and dropping funnel are installed, add tetraethoxysilane 62.5g (0.3 mole), tetrapropoxysilane 52.9g (0.2 mole), ethanol 62.5g and Virahol 52.9g, heat in oil bath while mixing, internal temperature is warming up to 50 ℃.In flask, stir, simultaneously with dripped in 10 minutes 0.1N aqueous hydrochloric acid 7.2g (water: 0.4 mole, hydrogenchloride: 7.2 * 10 ^-4Mole) and the mixing solutions of ethanol 7.2g, heat up again, under backflow, carry out slaking in 2 hours, obtain standby hydrolysis reaction liquid C11.

In addition, in the mixing solutions of 3-sulfydryl propyl trimethoxy silicane 39.3g (0.2 mole), methyltrimethoxy silane 40.9g (0.3 mole) and methyl alcohol 80.2g, 20～30 ℃ of internal temperatures down with 10 minutes dropping 0.1N aqueous hydrochloric acid 7.2g (water: 0.4 mole, hydrogenchloride: 7.2 * 10 ^-4Mole) and the mixing solutions of methyl alcohol 7.2g, 20～30 ℃ of following slakings of internal temperature 30 minutes, obtain standby hydrolysis reaction liquid C12 again.

In above-mentioned standby hydrolysis reaction liquid C11, add standby hydrolysis reaction liquid C12, mix, then 20～30 ℃ of internal temperatures add down 0.1N aqueous hydrochloric acid 1.8g (water: 0.1 mole, hydrogenchloride: 1.8 * 10 ^-4Mole) and the mixing solutions of ethanol 1.8g, and then in oil bath, heat, under backflow, carry out slaking in 2 hours.Then, add 1% ethanolic soln 9.4g (KF:1.62 * 10 of Potassium monofluoride ^-3Mole), part cohydrolysis and polycondensation are carried out in slaking 2 hours under refluxing again.

Then, under normal pressure with internal temperature degree of intensification to 80 ℃, pure composition is removed in distillation simultaneously, again under the reduced pressure of 30Torr (about 4kPa), internal temperature is warming up to 100 ℃, remaining pure composition and low boiling point component distillation are removed, filter then, obtain organopolysiloxane C1 (output: 127.5g, the yield: 92%) of water white transparency liquid state.

This organopolysiloxane C1, in an above-mentioned average group accepted way of doing sth (I), Y is a 3-sulfydryl propyl group, R ¹Be methyl, R ²Be propyl group, the mol ratio of employed each raw material (except the organic solvent), the weight-average molecular weight of being obtained by above-mentioned analytical results, mean polymerisation degree, an average group accepted way of doing sth, sulfydryl equivalent and the viscosity suitable with above-mentioned formula (I) are as described below.

The material molar ratio of " organopolysiloxane C1 ", an average group accepted way of doing sth and physics value

Material molar ratio:

HS(CH ₂) ₃Si(OCH ₃) ₃/CH ₃Si(OCH ₃) ₃/

Si(OC ₂H ₅) ₄/Si(OC ₃H ₇) ₄＝0.2/0.3/0.3/0.2

Catalyzer: HCl/KF/ water=0.00162/0.00162/0.9

Weight-average molecular weight: 1400

Mean polymerisation degree: 10.1

An average group accepted way of doing sth:

[HS(CH ₂) ₃] _0.2(CH ₃) _0.3Si(OCH ₃) _0.52(OC ₂H ₅) _0.71(OC ₃H ₇) _0.49O _0.89

Sulfydryl equivalent: measured value 696g/ mole, theoretical value 693g/ mole

Viscosity: 21.0mm ²/ s

[organopolysiloxane synthesis example 2]

In the flask of the capacity 1L that whipping appts, cooler condenser, thermometer and dropping funnel are installed, add tetraethoxysilane 41.7g (0.2 mole), tetrapropoxysilane 79.3g (0.3 mole), ethanol 41.7g and Virahol 79.3g, heat in oil bath while mixing, internal temperature is warming up to 50 ℃.Stir in flask on the limit, the limit with dripped in 10 minutes 0.5N aqueous hydrochloric acid 7.2g (water: 0.4 mole, hydrogenchloride: 3.6 * 10 ^-3Mole) and the mixing solutions of ethanol 7.2g, heat up again, under backflow, carry out slaking in 2 hours, obtain standby hydrolysis reaction liquid C21.

In addition, in the mixing solutions of 3-sulfydryl propyl-triethoxysilicane 47.7g (0.2 mole), methyltrimethoxy silane 40.9g (0.3 mole) methyl alcohol 40.9g and ethanol 47.7g, 20～30 ℃ of internal temperatures down with 10 minutes dropping 0.5N aqueous hydrochloric acid 7.2g (water: 0.4 mole, hydrogenchloride: 3.6 * 10 ^-3Mole) and the mixing solutions of methyl alcohol 7.2g, 20～30 ℃ of following slakings of internal temperature 30 minutes, obtain standby hydrolysis reaction liquid C22 again.

In above-mentioned standby hydrolysis reaction liquid C21, add standby hydrolysis reaction liquid C22, mix, then 20～30 ℃ of internal temperatures add down 0.5N aqueous hydrochloric acid 1.8g (water: 0.1 mole, hydrogenchloride: 9 * 10 ^-4Mole) and the mixing solutions of ethanol 1.8g, and then in oil bath, heat, under backflow, carry out slaking in 2 hours.Then, add 5% ethanolic soln 9.4g (KF:8.1 * 10 of Potassium monofluoride ^-3Mole), part cohydrolysis and polycondensation are carried out in slaking 2 hours under refluxing again.

Then, under normal pressure, internal temperature is warming up to 80 ℃, pure composition is removed in distillation simultaneously, again under the reduced pressure of 30Torr (about 4kPa), internal temperature degree of intensification to 100 ℃, is removed remaining pure composition and low boiling point component distillation, filtered then, obtain organopolysiloxane C2 (output: 136.7g, the yield: 94%) of water white transparency liquid state.

This organopolysiloxane C2, in an above-mentioned average group accepted way of doing sth (I), Y is a 3-sulfydryl propyl group, R ¹Be methyl, R ²Be propyl group, the mol ratio of employed each raw material (except the organic solvent), the weight-average molecular weight of being obtained by above-mentioned analytical results, mean polymerisation degree, an average group accepted way of doing sth, sulfydryl equivalent and the viscosity suitable with above-mentioned formula (I) are as described below.

The material molar ratio of " organopolysiloxane C2 ", an average group accepted way of doing sth and physics value

Material molar ratio:

HS(CH ₂) ₃Si(OC ₂H ₅) ₃/CH ₃Si(OCH ₃) ₃/

Si(OC ₂H ₅) ₄/Si(OC ₃H ₇) ₄＝0.2/0.3/0.2/0.3

Catalyzer: HCl/KF/ water=0.0081/0.0081/0.9

Weight-average molecular weight: 1460

Mean polymerisation degree: 10.0

An average group accepted way of doing sth:

[HS(CH ₂) ₃] _0.2(CH ₃) _0.3Si(OCH ₃) _0.3(OC ₂H ₅) _0.63(OC ₃H ₇) _0.78O _0.895

Sulfydryl equivalent: measured value 741g/ mole, theoretical value 728g/ mole

Viscosity: 22.5mm ²/ s

[organopolysiloxane synthesis example 3: relatively]

In the flask of the capacity 1L that whipping appts, cooler condenser, thermometer and dropping funnel are installed, add 3-sulfydryl propyl trimethoxy silicane 39.3g (0.2 mole), methyltrimethoxy silane 40.9g (0.3 mole), tetraethoxysilane 104.2g (0.5 mole), methyl alcohol 80.2g and ethanol 104.2g, 20～30 ℃ of bottoms stir in flask at internal temperature, the limit with dripped in 30 minutes 0.1N aqueous hydrochloric acid 16.2g (water: 0.9 mole, hydrogenchloride: 1.62 * 10 ^-3Mole) and the mixing solutions of methyl alcohol 16.2g, heat up again, under backflow, carry out slaking in 2 hours.

Then, add 1% ethanolic soln 9.4g (KF:1.62 * 10 of Potassium monofluoride ^-3Mole), part cohydrolysis and polycondensation are carried out in slaking 2 hours under refluxing again.Then, under normal pressure, internal temperature is warming up to 80 ℃, pure composition is removed in distillation simultaneously, again under the reduced pressure of 30Torr (about 4kPa), internal temperature is warming up to 100 ℃, remaining pure composition and low boiling point component distillation are removed, filter then, obtain organopolysiloxane C3 (output: 117.0g, the yield: 90%) of water white transparency liquid state.

This organopolysiloxane C 3, in an above-mentioned average group accepted way of doing sth (I), Y is a 3-sulfydryl propyl group, R ¹Be methyl, do not have OR ²(e=0), the mol ratio of employed each raw material (except the organic solvent), the weight-average molecular weight of being obtained by above-mentioned analytical results, mean polymerisation degree, an average group accepted way of doing sth, sulfydryl equivalent and the viscosity suitable with above-mentioned formula (I) are as described below.

The material molar ratio of " organopolysiloxane C3 ", an average group accepted way of doing sth and physics value

Material molar ratio:

HS(CH ₂) ₃Si(OCH ₃) ₃/CH ₃Si(OCH ₃) ₃/Si(OC ₂H ₅) ₄＝0.2/0.3/0.5

Catalyzer: HCl/KF/ water=0.00162/0.00162/0.9

Weight-average molecular weight: 1380

Mean polymerisation degree: 10.6

An average group accepted way of doing sth:

[HS(CH ₂) ₃] _0.2(CH ₃) _0.3Si(OCH ₃) _0.61(OC ₂H ₅) _1.08O _0.905

Sulfydryl equivalent: measured value 638g/ mole, theoretical value 651g/ mole

Viscosity: 20.5mm ²/ s

[organopolysiloxane synthesis example 4: relatively]

In the flask of the capacity 1L that whipping appts, cooler condenser, thermometer and dropping funnel are installed, add tetrapropoxysilane 132.2g (0.5 mole) and Virahol 132.2g, heat in oil bath while mixing, internal temperature is warming up to 50 ℃.Stir in flask on the limit, the limit with dripped in 10 minutes 1N aqueous hydrochloric acid 7.2g (water: 0.4 mole, hydrogenchloride: 7.2 * 10 ^-3Mole) and the mixing solutions of Virahol 7.2g, heat up again, under backflow, carry out slaking in 2 hours, obtain standby hydrolysis reaction liquid C41.

In addition, in the mixing solutions of 3-sulfydryl propyl-triethoxysilicane 47.7g (0.2 mole), Union carbide A-162 17.8g (0.1 mole) and methyl three isopropoxy silane 44.1g (0.2 mole), ethanol 65.5g and Virahol 44.1g, 20～30 ℃ of internal temperatures down with 10 minutes dropping 1N aqueous hydrochloric acid 7.2g (water: 0.4 mole, hydrogenchloride: 7.2 * 10 ^-3Mole) and the mixing solutions of Virahol 7.2g, 20～30 ℃ of following slakings of internal temperature 30 minutes, obtain standby hydrolysis reaction liquid C42 again.

In above-mentioned standby hydrolysis reaction liquid C41, add standby hydrolysis reaction liquid C42, mix, then 20～30 ℃ of internal temperatures add down 1N aqueous hydrochloric acid 1.8g (water: 0.1 mole, hydrogenchloride: 1.8 * 10 ^-3Mole) and the mixing solutions of Virahol 1.8g, and then in oil bath, heat, under backflow, carry out slaking in 2 hours.Then, add Potassium monofluoride 0.94g (KF:1.62 * 10 ^-2Mole), part cohydrolysis and polycondensation are carried out in slaking 2 hours under refluxing again.

Then, under normal pressure, internal temperature is warming up to 80 ℃, pure composition is removed in distillation simultaneously, again under the reduced pressure of 30Torr (about 4kPa), internal temperature is warming up to 100 ℃, remaining pure composition and low boiling point component distillation are removed, filter then, obtain organopolysiloxane C4 (output: 140.8g, the yield: 90%) of water white transparency liquid state.

This organopolysiloxane C4, in an above-mentioned average group accepted way of doing sth (I), Y is a 3-sulfydryl propyl group, R ¹Be methyl, do not have OCH ₃(c=0), R ²Be propyl group and sec.-propyl, the mol ratio of employed each raw material (except the organic solvent), the weight-average molecular weight of being obtained by above-mentioned analytical results, mean polymerisation degree, an average group accepted way of doing sth, sulfydryl equivalent and the viscosity suitable with above-mentioned formula (I) are as described below.

The material molar ratio of " organopolysiloxane C4 ", an average group accepted way of doing sth and physics value

Material molar ratio:

HS(CH ₂) ₃Si(OC ₂H ₅) ₃/CH ₃Si(OC ₂H ₅) ₃/

CH ₃Si(OC ₃H ₇) ₃/Si(OC ₃H ₇) ₄＝0.2/0.1/0.2/0.5

Catalyzer: HCl/KF/ water=0.0162/0.0162/0.9

Weight-average molecular weight: 1620

Mean polymerisation degree: 10.3

An average group accepted way of doing sth:

[HS(CH ₂) ₃] _0.2(CH ₃) _0.3Si(OC ₂H ₅) _0.39(OC ₃H ₇) _1.31O _0.9

Sulfydryl equivalent: measured value 803g/ mole, theoretical value 785g/ mole

Viscosity: 33.6mm ²/ s

Below, using above-mentioned acrylic resin that makes and organopolysiloxane, the preparation tackiness agent is expressed the embodiment and the comparative example that are applicable to blooming.Here, use following material as linking agent.

" コ ロ ネ one ト L ": the vinyl acetic monomer solution of the trimethylolpropane adduct of tolylene diisocyanate (solid component concentration 75%), Nippon Polyurethane Industry Co., Ltd.'s system, trade(brand)name

" TAZM ": TriMethylolPropane(TMP), three-β-'-aziridino propionic ester (liquid), mutual pharmaceutical worker Co., Ltd. system, trade(brand)name

In addition, silane compound as a comparative example uses following material respectively.

" KBM-803 ": 3-sulfydryl propyl trimethoxy silicane (liquid), Shin-Etsu Chemial Co., Ltd's system, trade(brand)name

" KBM-303 ": 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane (liquid), Shin-Etsu Chemial Co., Ltd's system, trade(brand)name

[embodiment 1～3 and comparative example 1～6]

(a) manufacturing of tackiness agent

Use is respectively the vinyl acetic monomer solution of the acrylic resin A1 that 100 parts polymerization example 1 obtains or the vinyl acetic monomer solution of the acrylic resin A2 that polymerization example 2 obtains in nonvolatile component, " the コ ロ ネ one ト L " as linking agent that cooperates the amount shown in the table 1 that is respectively therein, perhaps " コ ロ ネ one ト L " and " TAZM " and be respectively organopolysiloxane or the silane compound shown in the table 1 of the amount shown in the table 1, the preparation binder composition.Wherein, in the table 1, the use level (part) of linking agent " コ ロ ネ one ト L " is the amount of solids component.

Table 1

(b) making of the blooming of band tackiness agent

Use applicator that above-mentioned each binder composition is coated in polyethylene terephthalate film (" PET 3811 ", レ Application テ Star Network Co., Ltd. system, the trade(brand)name that the demoulding was handled; Be called dividing plate (separator)) demoulding treated side on, making dried thickness is 15 μ m, 90 ℃ dry 1 minute down, obtain flaky tackiness agent.Then; on the one side of the polarizing coating that carries out the clamping 3-tier architecture on the two sides of the polyvinyl alcohol polaroid that iodine is arranged with the protective membrane absorption orientation that comprises triacetyl cellulose; by fit face (tackiness agent face) with the opposite side of separator of the above-mentioned sheet tackiness agent that obtains of lamination; slaking 7 days under the condition of 23 ℃ of temperature, relative humidity 65% then obtains the polarizing coating with tackiness agent.In addition, the polarizing coating with these band tackiness agents of package encapsulation of band aluminium foil 60 ℃ of following recurring of temperature 6 days, promotes the variation in time that is caused by heat.

(c) making of optical laminate (glass of polarizing coating is pasting thing)

The polarizing coating of the band tackiness agent that makes in above-mentioned (b) (film that slaking obtained in 7 days under 23 ℃, 65%RH and the film that obtained in 6 days 60 ℃ of following slakings more thereafter) is being pasted at liquid crystal cell with glass substrate (" 1737 ", コ one ニ Application グ Co., Ltd. system with the binder layer side respectively in the mode of crossed nicols (Network ロ ス ニ コ Le), trade(brand)name) optical laminate is made on two sides.

(d) evaluation of the thermotolerance of optical laminate and humidity resistance

For the optical laminate that obtains in above-mentioned (c), carry out 300 hours oven test of keeping under the drying conditions of 80 ℃ of temperature, in addition, carry out in 60 ℃ of temperature, 300 hours hot resistance test of 90% time keeping of relative humidity, optical laminate after each test of visual inspection divides following 4 grades to estimate.The result is summarized in the table 2.

The judgement criteria of＜thermotolerance and humidity resistance 〉

◎: become flexible, peel off, appearance change such as foaming all there is not appearance.

Zero: become flexible, peel off, appearance change such as foaming almost do not occur.

△: become flexible, peel off, appearance change such as foaming a bit obviously.

*: become flexible, peel off, appearance change such as foaming occurs significantly.

(e) the re-workability evaluation of the blooming of band tackiness agent

The evaluation of re-workability is following to be carried out.At first, the polarizing coating of the band tackiness agent that will be made by (b) (film that slaking obtained in 7 days under 23 ℃, 65%RH and the film that obtained in 6 days 60 ℃ of following slakings more thereafter) is cut to the test film of 25mm * 150mm size respectively.Use adhering device (" ラ ミ パ Star カ one ", Off ジ プ ラ Co., Ltd. makes, trade(brand)name) then, this test film is attached to liquid crystal cell with on the glass substrate with its binder layer side, at 50 ℃, 5kgf/cm ²Carrying out 20 minutes autoclaves (490.3kPa) handles.Then, be formed in keeping under the atmosphere of 23 ℃ of temperature, relative humidity 50% after 24 hours sample and in 50 ℃ stove these two kinds of samples of the sample of keeping after 48 hours, under the atmosphere of 23 ℃ of temperature, relative humidity 50% polarizing coating being pasted test film with 180 ° of directions from this with 300mm/ minute speed peels off, observe the state of each glass baseplate surface, estimate according to following benchmark.The result together is shown in Table 2.

＜re-workability judgement criteria 〉

◎: glass pane surface does not occur bluring etc. fully.

Zero: glass pane surface occurs bluring etc. hardly.

△: the glass baseplate surface appearance is fuzzy etc.

*: the residual of tackiness agent appears in glass baseplate surface.

Table 2

By table 1 and table 2 as can be known, in acrylic resin and linking agent, cooperate among the embodiment 1～3 of the organopolysiloxane of stipulating among the present invention, thermotolerance, humidity resistance and re-workability all show good performance, in addition with the blooming of these band tackiness agents 60 ℃ of slakings after 6 days, thermotolerance, humidity resistance and re-workability also can obtain can roughly gratifying result.

With respect to this, cooperate in other the organopolysiloxane or the comparative example 1～6 of silane compound, be inadequate result in thermotolerance, humidity resistance and the re-workability.

Claims (11)

1, a kind of binder composition is characterized in that, contains

(A) acrylic resin,

(B) linking agent and

(C) organopolysiloxane of a following average group accepted way of doing sth (I) expression,

Y _aR ¹ _bSi(OCH ₃) _c(OC ₂H ₅) _d(OR ²) _e(OH) _fO _{(4-a-b-c-d-e-f)/2} ……(I)

In the formula (I), Y represents to have selected from mercapto, at least a kind organic group in epoxy group(ing), (methyl) acryloxy, thiazolinyl, haloalkyl and the amino;

R ¹The monovalence alkyl of representing the non-replacement of at least a kind of carbonatoms 1～8 that does not have an aliphatics unsaturated link(age);

R ²Alkyl or the methoxy-propyl of representing carbonatoms 3 and/or 4;

A, b, c, d, e and f are for satisfying the number of 0.01≤a≤1,0≤b＜2,0＜c≤2,0≤d≤2,0＜e≤2,0≤f≤1 and 0.1≤c+d+e≤2.5 and 2≤a+b+c+d+e+f≤3.

2, binder composition as claimed in claim 1, wherein, acrylic resin (A) contains following acrylic resin: with the structural unit from (methyl) alkyl acrylate is main component, contains the structural unit from (methyl) acrylic acid series compound with polar functional group.

3, binder composition as claimed in claim 2, wherein, polar functional group is the polar functional group that is selected from free carboxy, hydroxyl, amino and oxirane ring.

4, as each described binder composition in the claim 1～3, wherein, linking agent (B) contains the isocyanic ester based compound.

5, as each described binder composition in the claim 1～4, wherein, in the above-mentioned average group accepted way of doing sth (I) of expression organopolysiloxane (C), Y is the organic group with sulfydryl or epoxy group(ing).

6, as each described binder composition in the claim 1～5, wherein, in the above-mentioned average group accepted way of doing sth (I) of expression organopolysiloxane (C), b is a positive number, R ¹Be methyl, R ²Be propyl group or sec.-propyl.

7, as each described binder composition in the claim 1～6, wherein, in the above-mentioned average group accepted way of doing sth (I) of expression organopolysiloxane (C), d is a positive number.

8, as each described binder composition in the claim 1～7, wherein, the mean polymerisation degree of organopolysiloxane (C) is 3～100.

9, a kind of blooming with tackiness agent is characterized in that, at least one face of blooming is provided with the binder layer that is formed by each described binder composition in the claim 1～8.

10, the blooming of band tackiness agent as claimed in claim 9, wherein, blooming is selected from polarizing coating and phase retardation film.

11, the blooming of band tackiness agent as claimed in claim 10, wherein, blooming contains pasting at least one face of polaroid and comprises acetyl fibre prime system resin or noncrystalline cyclic polyolefin is the polarizing coating of the protective membrane of resin.